Components for hair dyeing compositions

ABSTRACT

A GROUP OF N-SUBSTITUTED ALKYL DERIVATIVES OF NITROAMINOBENZENES WHICH ARE CHARACTERIZED BY THE FACT THAT THE ALKYL GROUP CARRY FURTHER SUBSTITUENTS SUCH AS -O-ALKYL, -NH-CO-ALKYL, -NH-CO-HYDROXYALKYL, -NHCO-ARYL, -NHSO2-ALKYL, -NHSO2-ARYL, -NHCONH2,   -NH-CO-ALKYL; -NH-C(=S)-NH2; -CO-ALKYL; -CN; -SO2-NH2;   -SO2-NH-ALKYL; -SO2-NH-HYDROXYALKYL; -SO2-N(-ALKYL)-ALKYL   -SO2-N(-HYROXYALKYL)-ALKYL;   -SO2-N(-HYDROXYALKYL)-HYDROXYALKYL   AND -SO2-ALKYL; THESE ARE USEFUL AS DYES OR DYE INTERMEDIATES THAT ARE PARTICULARLY SUITABLE FOR DYEING HAIR.

United States Patent Ofice 3,629,330 Patented Dec. 21, 1971 3,629,330COMPONENTS FOR HAIR DYEING COMPOSITIONS Frederick Brody, New York, N.Y.,Alexander Halasz, Norwalk, Conn, and Miles S. Bil, Forest Hills, N.Y.,assignors to Clairol Incorporated, New York, N .Y. No Drawing. Filed May24, 1965, Ser. No. 458,443 Int. Cl. C07c 103/33, 127/14, 143/78 US. Cl.260-553 A 33 Claims ABSTRACT OF THE DISCLOSURE A group of N-substitutedalkyl derivatives of nitroaminobenzenes which are characterized by thefact that the alkyl group carry further substituents such as --Oalkyl,NHCO-alkyl, NHCOhydroxyalkyl, NHCOaryl, NHSO -alkyl, NHSO aryl, NHCONHand SO alkyl; these are useful as dyes or dye intermediates that areparticularly suitable for dyeing hair.

This invention relates to a novel group of alkyl derivatives ofnitroaminobenzenes that are particularly suitable as dye intermediatesor for dyeing keratinaceous materials. More particularly, it relates tosaid derivatives and compositions containing the same which may be usedto dye living human hair on the head or as dye intermediates inpreparing such dyes.

A variety of nitrophenylenediamine derivatives have been suggested foruse in the prior art as hair dyes. These, however, have been found inpractice to offer many disadvantages. Nitrophenylenediamine dyes havingno substituents on the amino nitrogens have only a yellow or orangeshade. This is a disadvantage, since it is the red, blue and violetshades that are necessary for blending colors to arrive at naturallooking shades.

The simple alkyl-substituted nitrophenylenediamine derivatives whereinonly the simple alkyl substituents (e.g., methyl, ethyl) are on one orboth amino nitrogens are insufficiently soluble or dispersible in Water.Moreover, some dyes of this class tend to sublime readily when exposedto heat (e.g., body heat or sunlight). The dyeings with these dyes,thus, become weaker and off-shade on wearing.

It has also been suggested to employ, as hair dyes, compounds of thetype discussed above which have ionizable substituents on the alkylgroup bonded to the amino nitrogen. Substituted alkyl groups of thistype include CH CO H, -(CH SO H and CH CH NR +CI. However, dyes havingthe groups have generally low affinity to hair under the mild conditionsrequired. Dyes having the CH CH NR +Clgroup may have good aflinity forhair but tend to dye unlevel, to be rubbed 01f readily and to stain theskin.

It has further been suggested to introduce such side chains as CHZCHZOH,and CH CH NH and -CH CONH into the nitrophenylenediamine dyes as a chiefgroup determining the characteristics of the dye. These groups tend tounduly raise the hydrophilic character of the dye when too many of themare present, resulting in poor dyeing. This is due to the fact that thedye would tend to stay in the dye bath rather than go onto the hair.Moreover, dyes having the aminoalkyl radical are high in basicity whichmakes the dye more soluble in acid media and less likely to go onto thehair from such media.

It has now been found that the disadvantages of the prior art dyes notedabove are avoided through the use of an alkyl derivative ofnitrophenylenediamines, defined in more detail below. Moreover, it hasalso been found that these may be readily prepared from certain alkylderivatives of nitroaminobenzenes, also defined below.

It is accordingly an object of the present invention to provide a groupof novel compounds that are suitable for use in dyeing keratinaceousmaterial, and particularly human hair.

It is another object of the present invention to provide a dyeintermediate suitable for synthesizing a dye that may be employed indyeing keratinaceous material, and particularly human hair.

It is further object of the present invention to provide a compositionsuitable for dyeing keratinaceous material, and particularly livinghuman hair, which incorporates therein one or more of said novelcompounds.

It is still a further object of the present invention to provide amethod for dyeing keratinaceous materials, and particularly living humanhair which utilizes said composition mentioned in the above objects.

It is still another object of the present invention to provide novelalkyl derivatives of nitrophenylenediamines which avoid thedisadvantages of similar type compounds known in the prior art andmentioned above when used in dyeing human hair.

Other and more detailed objects will be apparent from the followingdescription and claims.

The above objects of the present invention are obtained by means ofcompounds of the following formula and particularly hair substantivedyes of this formula:

I. ITIHR wherein Y and Z are selected from the group consisting of NOand NR R at least one of said Y and Z being NO and wherein R R and R areselected from the group consisting of hydrogen, alkyl, hydroxyalkyl andthe radical -alkyleneX, at least one of said R R and R being the radical--alkyleneX, in which the divalent radical alkylene may be straightchain or branched chain and may contain up to 4 carbon atoms; and X isselected from the group O-alkyl, -NHCOalkyl, NHCOhydroXyalkyl,NHCO-aryl, NHSO -alkyl, -NHSO aryl, NHCONH CN, SO NH droxyalkyl;

and --SO alkyl; the alkyl and hydroxyalkyl portions of these groupscontaining 1 to 6 carbon atoms, and preferably 1 to 3 carbon atoms.

In the compounds of Formula I in which both Y and Z are -NO the abovedefinition provides that R is -alkylene-X. Although these have some useas dyes, they are principally useful as intermediates in preparing alkylderivatives of nitrophenylenediamines. On the other hand, compounds ofFormula I which are especially suitable as dyes are those compounds inwhich one of Y and Z is NO and the other is -NR R wherein R and R havethe same significance ascribed to them above.

When R R or R in Formula I above is an alkyl radical, it may be of anycarbon-chain length and may be either straight chain or branched chain.As a practical matter, however, the alkyl radical will rarely exceed 8carbon atoms. In the preferred form of the invention, the alkyl radicalsare lower alkyl radicals, and particularly alkyl radicals having from 1to 4 carbon atoms. By way of example, the following specific alkylradicals may be mentioned: methyl, ethyl, propyl, isopropyl, n-butyl,sec.- butyl, tert.-butyl, n-amyl, n-hexyl, and Z-ethylhexyl.

Similarly, when R R or R of Formula I are bydroxyalkyl radicals, thealkyl moiety of these radicals may be of any carbon-chain length andlikewise may be either straight chain or branched chain. Again, however,as a practical matter, they will rarely exceed 8 carbon atoms, andpreferably they will be lower alkyl groups containing from 1 to 4 carbonatoms.

Moreover, the number of hydroxy groups that will be contained in saidhydroxyalkyl radicals will also vary. For the most part, there will be amaximum of 3 hydroxy groups.

The following list exemplifies the hydroxyalkyl groups which areincluded within the definition of R R and R of Formula I above:hydroxymethyl, Z-hydroxyethyl, 3- hydroxypropyl, 2,3-dihydroxypropyl and4-hydr-oxybutyl. The aryl group may be unsubstituted or may contain anyof a variety of substituents. Typical of the substituents that can bementioned are lower alkyl, halogen, hydroxyalkyl, lower alkoxy, nitro,dialkylamino, carbamoyl, sulfamoyl, etc.

Where the aryl radical is a substituted phenyl radical, the substituentsmay occupy any position in the benzene nucleus. When the aryl radical isa naphthyl radical, the substituents may occupy any of the or or [3positions. In the preferred form of the invention, this aryl radical isa hydrocarbon radical, and more particularly a phenyl radical or a loweralkyl substituted phenyl radical.

By way of illustrating the compounds of this invention of the type inwhich at least one of said R R and R is the radical alkyleneNHCOaryl or-alkylene-- NHSO -aryl, the following examples of aryl may be mentioned:phenyl, o-, m-, p-tolyl, m-chlorophenyl, mand p-anisyl, p-ethoxyphenyl,m-hydroxymethylphenyl, mnitrophenyl, p-dimethylaminophenyl,m-carbamoylmethyl, m-sulfamoylmethyl, l-naphthyl, Z-naphthyl,3-hydroxy-2 naphthyl, 8-methoxy-1-naphthyl.

The compounds of the present invention may be prepared by various knownmethods which depend on the nature and position of the substituent--alkyleneX in Formula I.

In the case where R has the value alkyleneX in Formula 1, thesecompounds are generally prepared by first reacting2,4-dinitrochl0robenzene with a suitable amine, NH -alkyleneX. This isaccomplished by heating one mole of the former with one or more moles ofthe latter, in alcohol, aqueous alcohol, or an organic solventcontaining an acid binder, such as sodium bicarbonate, sodium acetate,calcium carbonate or an additional mole of the amine, at reflux forperiods ranging from /2 hour to 6 hours. This gives an N-substituted2,4-dinitroaniline (Formula A below).

In the next step one of the nitro groups is preferentially reduced togive either a Z-nitro-p-phenylenediamine or a4-nitro-o-phenylenediamine, depending on the reduction method used. Inthe former case the reduction is carried out essentially by the methodof U-Sa Pat. 3,088,978,

namely by catalytic hydrogenation in an organic solvent in the presenceof mineral acid; the acid salt of the substituted2-nitro-p-phenylenediamine (Formula B below) precipitates out of thereaction mixture, and the free base is recovered therefrom bybasification. In order to obtain a 4-nitro-o-phenylenediamine, one canreduce the dinitroaniline (Formula A below) by means of a slight excessof sodiumpolysulfide in aqueous alcoholic medium by heating at about C.for about 10 to 15 minutes; the product (Formula C below) precipitatesout.

From the substituted nitrophenylenediamines described above, one canproceed to further variations of Formula I in which R and R are alkyl orhydroxyalkyl groups by reaction with the appropriate alkyl orhydroxyalkyl halide, sulfate or tosylate or an alkylene oxide, forexample, with ethyl iodide, dimethyl sulfate, methyl tosylate, ethylenechlorohydrin or ethylene oxide, by known methods. Either one or twoalkyl or hydroxylalkyl groups may be introduced by varying theproportion of the reagent used, the course of the reaction beingconveniently followed by chromatogram, and stopped when the appropriatedegree of substitution has been reached. Similarly, R and R may bedifferent alkyl or hydroxyalkyl groups, which are introducedsequentially by reaction first with R -hal and then with R hal (halbeing a halogen atom or its equivalent sulfate or tosylate group).

When in the general Formula I, it is desired that R and/ or R; be thesubstituted alkyleneX, the dye may be conveniently prepared from a2-nitro-p-phenylenediamine or a 4-nitro-o-phenylenediamine (e.g.,Formula D below) in which R is already present. This is reacted with anappropriate X-alkylenehal, in which hal represents a chlorine, bromineor iodine atom. Depending on the reactivity of the Xalkylenehal and thenumber of X-alkylene groups to be introduced (whether one or two), oneuses varying proportions of the reagent, from one mole to a largeexcess.

The reaction is carried out in an organic solvent or aqueous organicsolvent at temperatures varying from room temperature to about C., andfor times varying from 1 to 20 hours. The solvent, temperature and timeof reaction selected depend in part on the activity of the Xalkylenehalused. For example, highly reactive Xalkylenehal compounds, such aschloroacetonitrile, are reacted at low temperatures, in a low boilingsolvent, such as ethanol, for short times, say 1 to 2 hours. TheXalkylene-hal compounds of low activity, such as chloroethyl ethylether, are reacted in a high boiling solvent, such as amyl alcohol, atreflux temperature for at least 8 hours.

In any case, the extent of reaction is preferably followed bychromatogram in which can be seen the proportion of unreacted,monosubstituted and disubstituted com ponents, which can bedistinguished by their colors. The reaction is stopped at the desiredstage, and the mixture worked up as usual. Significant amounts ofunreacted starting material may be removed as the Schiffs base withbenzaldehyde.

An alternate method for introducing alkylene-X groups is to react anitrophenylenediamine (e.g., Formula D below) with a compound having anactivated double bond. In this case the -X moiety generally is anelectron attracting group which serves to activate the double bond.Examples of reactants of this character include acrylonitrile, vinylmethyl ketone, and methyl vinyl sulfone. The reaction is carried out byusing equimolecular amounts of the two materials, in alcohol or aqueousalcohol containing a small amount of acetic acid as catalyst and heatingto reflux for 3 to 10 hours. By this means only one alkyleneX willgenerally be introduced. For the introduction of two such groups, alarge excess of the unsaturated reactant may be used, serving also asthe solvent. After one group -alkylene-X has been introduced, it ispossible to introduce a different alkyl, hydroxyalkyl or -alkylene-Xgroup by reaction NR R (b) When R and/ or R of Formula I is NEE; NHR1N0, JNO2 alkylene-X N N (alkylene-X) z (c) When activated double bondreactant is employed:

(D) NHRi NHRr I NO2 I I l l NH, NII-(l)(l3X I C=OX I I R3 hal l IYIHR1IIIHRI NO; NO;

I I I I l l N(CC-X) N l I z While the above procedures are generallyuseful for the preparation of the dyes of this invention, certainalternate routes may be suitable in specific cases. Thus, when -X isacylamido, one may first prepare an N-aminoalkyl derivative of anitrophenylene-diamine, and subsequently acylate and free aliphaticamino group by means of an acid anhydride, acid chloride, alkanesulfonylchloride, arylsulfonyl chloride, or chloroformic ester using knownmethods. Or, by reacting 2,4-dinitrochlorobenzene with a diaminoalkane,one can obtain an N-aminoalkyl-2,4-dinitroaniline, which may be acylatedand one of the nitro groups reduced and so forth, as described above.

When X is a ureido group, NHCONH one may again prepare the aminoalkylderivatives mentioned above, and either react them with potassiumcyanate in a solvent or fuse them with urea for conversion of the freeamino group to the ureido. For introducing the thioureido group, NHCSNHone may react the aminoalkyl derivatives with carbon disulfide andcaustic to form the dithiocarbonate; this is converted to theisothiocyanate (e.g., by reaction with ethyl chloroformate), and this inturn reacted with dry ammonia.

In the case where X is a sulfamoyl or a substituted sulfamoyl group, itis convenient to first react 2,4-dinitrochlorobenzene with anaminoalkanesulfonic acid (such as taurine), thereby obtaining anN-sulfoalkyl-2,4-dinitroaniline. This may be converted by known methods,as with PCl to the N-ch10rosulfonylalkyl-2,4-dinitroaniline which byreaction with ammonia, an alkylamine or a hydroxyalkylamine forms thecorresponding sulfamoylalkyl derivative of 2,4-dinitroaniline.

The dyes embodied in the present invention have many advantages over theprior art dyes utilized in this field. As compared withnitrophenylenediamine dyes having no substituents on the nitrogens,which are yellow or orange in shade, the dyes of this invention show awide range of shade, from yellow to bluish violet.

As compared with the dyes having only unsubstituted alkyl groups on thenitrogen (such as simple methyl, ethyl), the dyes of this invention aremore soluble in water, or more readily dispersible. They can thus givemore concentrated dye baths and therefore much stronger dyeings on hair.Also, as previously mentioned, the dyes of this character wherein only Hor unsubstituted alkyl groups are bonded to nitrogen tend to sublimereadily, when exposed to heat (e.g., body heat or sunlight) and thus tobecome weaker and olf-shade on wearing. In contrast, the dyes havingionizable substituents on the alkyl group, i.e. where the radical on thenitrogen is (CH SO H, Or -CH CH NR +CI for example, which ionize inwater to give the radicals -CI-I CO (CH SO or CH CH NR respectively, thedyes of this invention have much higher aifinity to hair without at thesame time dyeing the hair unlevely, rubbing off, or staining the skin.

With regard to prior art dyes having nonionic substituted alkylradicals, such as --CH CH CH,

-CH CH OCH CH CH 0H -CH CH NH and CH CONH the advantages of the presentdyes vary. For example, an acylated aminoalkyl side chain, such as CH CHNHCOR or This is because dye aifinity and wet fastness depend on havingan optimum of hydrophilic character. Thus, too

low a hydrophilicity (unsubstituted alkyl) gives low solu bility andpoor dyeing, but too high a hydrophilicity also gives poor dyeing, sincethe dye then tends to remain in the dye bath rather than going on thehair. A free hydroxy or amino group has more hydrophilic character thanalkoxy or acylamido and could in fact be too hydrophilic for the purposeof dyeing hair.

A further disadvantage of the aminoalkyl radical is its high basicitywhich makes the dye more soluble in acidic media and less likely to goon hair therefrom. This disadvantage is removed in the case of all ofthe present acylamido derivatives, i.e., alkyl substituted by NHCOR,NHCOAr, NHSQ R, NHCONH NHCO R, NHCSNH Another comparison may be madedirectly between the known sulfonic acid dyes (having (CH SO H) and thepresent sulfonarnide dyes (having SO NH SO NHR, or SO NRR). As discussedabove, the sulfonic dyes are anionic, with low general affinity whencompared to the sulfonamides of this invention.

The dyes of the present invention can be employed to prepare basic,neutral or acidic dye compositions and because of their stability, maybe used in conjunction with oxidation dyes. Furthermore, they maylikewise be included in hair dyeing compositions which contain otherdirect dyeing dyes that also may or may not contain an oxidation dye. Avariety of direct dyeing dyes are known in the prior art which areuseful for this purpose. They include other nitro dyes, azo dyes,anthraquinone dyes, etc. By way of illustration, any of the nitro dyesdisclosed in the following U.S. patents may be used in conjunction withthe present nitro dyes: 2,750,326; 2,750,327; 3,088,- 877; 3,088,878 and3,088,978.

The dye compositions of this invention have in general the advantagethat they are stable on storage. For example, when they are stored inthe dark at 50 C. for a period of 3 months and then dyed on hair bymethods described below, they show essentially no change in shade orstrength of dyeing, as compared to the same compositions appliedinitially, before storage. Stability on storage is of great commercialimportance, since dye compositions on the market are likely to be heldon the shelf for periods up to several years, sometimes at high ambienttemperatures.

The pH of the dye compositions of this invention can vary from about 2.5to 11. In the acid range the pH of about 3.5 to 6 is suitable. It ispreferred, however, that the compositions be in the alkaline range, andparticu larly at a pH of about 7.5 to 10. Any selected waterdispersible,compatible, alkalizing agent (if it is desired to have the compositionsin the alkaline range) can. be used to give the desired pH. The quantityof the alkalizing agent employed can vary over a wide range depending onthe dye and particular alkalizing agent employed and the desired pH.Illustratively, the alkalizing agent can vary from less than about 0.1%to about 10%, and preferably from about 0.25% to about 5% by weight ofthe composition.

The alkalizing agent is selected so that it will not interfere (i.e., iscompatible) with the dye employed, and will not precipitate the dye orintroduce any possibility of toxicity under the conditions of use, orinjure the scalp at its ultimate concentration in the composition to beapplied to the keratinaceous material. A preliminary test of someselected alkalizing agent can be made to note its compatibility with thedye or to discover possibility of toxicity or injury.

Ammonium hydroxide, because of its freedom from toxicity over a wideconcentration range and its economy, is an acceptable alkalizing agent.HoWever, there can be used in place of, or together with, ammonia anyother compatible ammonia derivative as an alkalizing agent, such as analkylamine, such as ethylamine, dipropylamine, or triethylamine, analkanediamine, such as 1,3-diaminopropane, an alkanolamine, such asethanolamine or diethanolamine, a polyalkylenepolyarnine, such asdiethylenetriamine, or a heterocyclic amine, such as morpholine.

Also, as alkalizing agent, any alkaline earth hydroxide, for example,calcium hydroxide or magnesium hydroxide, can be used up to the limit ofits water solubility and at any concentration that fails to produce aprecipitate with any of the components of the composition. The dissolvedalkaline earth hydroxides are preferred over the alkali metalhydroxides, such as sodium hydroxide or potassium hydroxide, orcarbonates, such as sodium carbonate and bicarbonate, any of which. canalso be used so long as their ultimate concentration in the final dyeingsolution is below that which might possibly irritate the scalp.

The alkalizing component of choice, however, is a water-soluble organicamine of low volatility (B.P. higher than about C.) having less thanabout 12 carbon atoms, such as n-propylamine, isobutylamine,2-ethylbutylamine, diethylamine, triethylamine. Particularly suited asthe alkalizing agent are the following: (A) primary aliphatic diamines,such as ethylenediamine; 1,2- diaminopropane; 1,3-diaminopropane;diethylenetriamine; triethylenetetramine; 2,2'-iminodipropy1amine;3,3-iminodipropylamine; and bis-hexamethylenetriamine; (B)alkanolamines, such as ethanolamine; isopropanolamine; diethanolamine;di-isopropanolamine; triethanolamine; triisopropanolamine;N-methyldiethanolamine; diisopropylethanolamine;dimethylisopropanolamine; 2 amino- Z-methylpropane 1,3 diol;tris(hydroxymethyl)methylamine and the like, which may also have aphenyl substituent, e.g., N-(Z-hydroxyethyl)aniline; N-methyl-N-Z-hydroxyethyl) aniline; N,N-bis 2-hydroxyethyl) aniline; and (C)heterocyclic amines, such as morpholine, N-methylmorpholine,N-ethylmorpholine, N-hydroxyethylmorpholine, N-phenylmorpholine,piperidine, N-hydroxyethylpiperidine, and piperazine.

The pH of the composition may be adjusted with any inorganic or organicacid or acid salt which is compatible with the composition and will notintroduce toxocity under its conditions of use, especially when acidcompositions are desired. Illustrative of acids or acid salts there canbe mentioned: sulfuric, formic, acetic, lactic, citric or tartaric acid,or ammonium sulfate, sodium dihydrogen phosphate, or potassiumbisulfate.

Water-soluble surface active agents can also be employed in the dyeingcompositions utilized in this invention. These can be anionic, non-ionicor cationic. Illustrative of the various types of water-soluble surfaceactive agents there can be mentioned: higher alkylbenzenesulfonates;alkylnaphthalenesulfonates; sulfonated esters of alcohols and polybasicacids; taurates; fatty alcohol sulfates; sulfates of branched chain orsecondary alcohols; alkyl dimethylbenzyl ammonium chlorides; and thelike. Illustrative of specific surfactants there can be mentioned:lauryl sulfate; polyoxyethylene lauryl ester; myristyl sulfate; glycerylmonostearate; sodium salt of palmitic methyl taurine; cetyl pyridiniumchloride; lauryl sulfonate; myristyl sulfonate; lauric diethanolamide;polyoxyethylene stearate; stearyl dimethyl 'benzyl ammonium chloride;dodecyl benzene sodium sulfonate; nonyl naphthalene sodium sulfonate;dioctyl sodium sulfosuccinate; sodium N-methyl-N-oleoyl taurate; oleicacid ester of sodium isothionate; sodium dodecyl sulfate; the sodiumsalt of 3,9- diethyl tridaconol-6-sulfate and the like. The quantity ofwater-soluble surface active agent can vary over a wide range, such asthat of from about 0.25% to 15% and preferably from about 0.25 to 10% byWeight of the composition.

A thickening agent can also be incorporated in the present dyeingcomposition which may be one or several of those commonly used in hairdyeing, such as sodium \alginate or gum arabic, or cellulosederivatives, such as methylcellulose, or the sodium salt ofcarboxymethylcellulose, or acrylic polymers, such as polyacrylic acidsodium salt, or inorganic thickeners, such as bentonite. The quantity ofthickening agent can vary over a wide range, such as that of from about0.1% to 20% and preferably from about 0.5% to 5% by weight.

Tinctorially effective quantities of the novel nitro dyes in thecompositions of this invention can also vary over a wide range, such asthat of about 0.01% to greater than about e.g., by weight of thecomposition, and preferably from about 0.01% to about 2% by weight. Thewater content of the composition is ordinarily the major constituent andcan vary over a wide range dependent in large measure on the quantity ofother additives. Thus, the water content can be as little as 10%, andpreferably from about 70% to 99%.

The dyeing compositions of this invention are preferably aqueouscompositions. The term aqueous composition is used herein in its usualgeneric sense as embracing any water-containing composition embodied inthe invention. This includes true solutions of the dye in an aqueousmedium, ether alone or in conjunction with other materials, which arealso dissolved or dispersed in the aqueous medium. The term aqueouscomposition also encompasses any mixture of dye With the aqueous mediumeither alone, or together with other ingredients. The dye may becolloidally dispersed in the medium or may merely be intimately mixedtherein.

The term aqueous medium as used herein, includes any medium whichcontains water. Thus, the aqueous medium may be an aqueous alkaline,aqueous neutral or aqueous acid medium. Moreover, the aqueous medium maycomprise water and a solvent, e.g., ethanol. The latter may be employedas a common solvent to enhance the solution of the dye or some otherorganic material.

The aqueous compositions of this invention may take many forms. Thus,they may be thin or thick flowable liquids, pastes, gels, etc.

Typical dyeing compositions of the various classes described above areset forth below:

1. ALKALINE COMPOSITIONS General Preferred range range Dye, percent 0.01-5 0. 01-2 Surface active agent, percent. 0. 25-10 0. 25-5 Alkali,percent 0. 1-10 0. 25-5 Thickening agent, percent 0. 120 0. 5-3 Acidadded to, pH 7-11 7. 5-9. 5

Water to 100%.

Any of the dyes, surface active agents, a-lkalies, thickening agents,acids and combinations thereof set forth above may be used in theproportions specified in the table immediately above.

(2) ACID COMPOSITIONS (3) OXIDATION DYE COMPOSITIONS The novel nitrodyes utilized in this invention are generally compatible with oxidationdyes. Accordingly, they can be used in oxidation dye compositions.Suitable compositions contain 15% ammonia, 23% hydrogen peroxide or ureaperoxide; 0.005% to 2% oxidation dye components; 0.001% to 3% Compound Ias defined above, as well as surfactants, thickeners, etc. By way ofillustration in this connection, the following oxidation dye componentscan be utilized in formulating this composition: 0- phenylenediamine,m-phenylenediamine, p-phenylenediamine, p-toluenediamine,nitro-p-phenylenediamine, 4- nitro-o-phenylenediamine,p-aminodiphenylamine; 4,4- diaminodiphenylamine; 4,6 dinitro 2aminophenol; 4- nitro-2-aminophenol; 2,4-diaminoanisole, hydroquinone,

resorcinol, p-aminophenol; 1,2,4-trihydroxybenzene; 1,2,4-triacetoxybenzene.

The dyeing compositions of this invention can be prepared by theconventional methods used in the hair dyeing art. Thus, they can beprepared by dissolving or suspending the dye in water in the desiredconcentration. Water miscible organic solvents can be employed tofacilitate solution of the dye; in this event, the dye can be dissolvedfirst in the solvent and then diluted with water. The dispersion of thevarious ingredients can also be facilitated by heating the compositionat temperatures varying from 40 C. to 110 C., either before dilutionwith water or afterwards.

The dyeing compositions of this invention can be applied to hair by theconventional techniques used in the art. Illustratively, when applied toliving hair on the human head, the compositions can be applied to thehair with a brush, sponge, or other means of contact, such as dippinguntil the hair is properly saturated with the composition.

The reaction time or time of contact of the dyeing composition with thehair is not critical and can vary over a Wide range used in the hairdyeing art, such as periods of about 5 minutes to about 2 hours, andpreferably from about 15 minutes to about minutes. The dyeingtemperature can vary over wide limits as is conventional in the art.Thus, the dyeing temperature can vary from about room temperature, e.g.,about 20 C. to above about 60 C., and preferably from about 20 C. toabout 45 C.

The following examples are further illustrative of the presentinvention. It is to be understood, however, that the invention is notlimited thereto.

Example 1 NHCHzCH OCH:

A solution of 37.5 g. 2-methoxyethylamine in 200 ml. water was heated toreflux, and 50 g. 2,4-dinitrochlorobenzene was slowly dropped in. Thissolution was then refluxed for an additional hour, and the mixture wascooled and filtered. The filter cake was then washed with water: Yield,58.8 g. of a product having the above structural formula. This had amelting point of 143-7 C.

Example 2 lTIHCH OH OCH;

To a solution of 30 g. N-(Z-methoxyethyl)-2,4-dinitroaniline in 500 ml.50% isopropanol, maintained at a temperature of C., was added 50 ml. ofan aqueous solution containing 31.5 g. 60% sodium sulfide flakes and 8.2g. sulfur. The resulting solution was stirred for one hour, then pouredover ice. The product was then filtered off and washed. This synthesisgave a yield of 8.2 g. of yellow crystals of the product of the aboveformula which had a melting point of 10l6 C.

Example 3 ITIHCHzC H2O CH3 A mixture containing:

28 g. N-(Z-methoxyethyl)-2,4-dinitroaniline 150 ml. isopropanol 2. g.platinum-on-charcoal was hydrogenated at atomospheric pressure until 3molar equivalents of hydrogen were taken up. A precipitate was formedwhich was filtered off and treated with 600 ml. boiling water in orderto dissolve the sulfate salt of the product. The hot slurry was filteredand the filtrate was cooled and made basic with ammonia. The product,which has the above structure, and which was in the form of reddishcrystals, was filtered off. The yield was 3.3 g.

Example 4 IfHomomooHa l uomonzoroz A mixture of:

13 g. N -(2-methoxyethyl)-2-nitro-p-phenylenediamine 50 ml. water 300ml. isopropanol 200 ml. chloroethanol was heated at reflux. Over aperiod of two hours, 320 g. of aqueous NaOH was dropped into thereaction mixture. The excess chloroethanol was steam-distilled off. Theresidue was then extracted with ethyl acetate. The solution was thenconcentrated and, on standing in the cold, there was obtained 9 g. ofviolet crystals having a melting point of 64-5 C. This product has theabove structure.

Example 5 ITIHCH CH O 011 011 To a mixture of:

400 ml. isopropanol g. Na CO g. Z-ethoxyethylamine at reflux was addedover a period of /2 hour 101 g. of 2, 4-dinitrochlorobenzene. Thismixture was heated for one hour, cooled and filtered. The productobtained was then washed with water. There was recovered 124 g. of theproduct of the above structure, having a melting point of 81-2 C.

1 Example 6 Y IIIHCH CH O CH CH;

To a mixture of 30.7 g. N-(2-ethoxyethyl)-2,4-dinitroaniline and 175 ml.isopropanol heated at 70-80 C., there was added, while stirring and overa period of one hour, a solution of 31.5 g. of 60% sodium sulfideflakes, 8.2 g. sulfur and ml. water. The reaction mixture was cooled,filtered and the product was recrystallized from water. This product,having the above structural formula, was in the form of yellow crystalsand had a melt ing point of 82 C.

Example 7 J3|IHCHgCH OCH CHa I NH -A mixture containing:

1 g. 5% platinum-on-charcoal 12.7 g.N-(Z-ethoxyethyl)-2,4-dinitroaniline ml. ethanol 30 g. 50% sulfuric acidwas hydrogenated at 50-90 p.s.i. until 3 molar equivalents of hydrogenwere absorbed. The mixture was filtered and the precipitate extractedwith hot water for removal of the sulfate product. The extract aftercooling was made basic with ammonia. The product, which has the abovestructure, was filtered off and recrystallized from ethanol. This was inthe form of red crystals and had a melting point of 86 C.

EXAMPLE 8 IITHCH2CHZOCHZCH3 I HOH CH OHM To a solution N-(2-ethoxyethyl)-2-nitro-p-phenylenediamine in 50 ml. ethanol, 150 ml.chloroethanol was added. Over a period of 2 hours at reflux, there wasadded 200 g. of 25% aqueous NaOH. After steam-distilling off the excesschloroethanol, the residual mixture was extracted with ethyl acetate. Onevaporation of the solvent, there was obtained a violet dye of themelting point 52-3 C.

Example 9 IIIHCHQ l lHCH cH OCH A mixture of 16.7 g. N-methyl-2-nitro-p-phenylenediamine, 10.0 g. sodium carbonate, 9.5 g.2-chloroethyl methyl ether, and 150 ml. n-amyl alcohol was heated atreflux for 10 hours. At this point a test portion examined by paperchromatography showed the presence of reddish violet product and asignificant amount of the starting primary amine N-methyl 2nitro-p-phenylenediamine; however, no tertiary amine by-product waspresent. The reaction mixture was steam-distilled and evaporated todryness, and the residue dissolved in ml. ethanol. Then, for removal ofthe unreacted primary amine, 10.6 g. benzaldehyde was added, the mixtureheated for 1 hour, and the precipitated benzal derivative of N-methyl-2-nitro-p-phenylenediamine filtered off. Excess benzaldehyde was removedfrom the filtrate by steam distillation, and the desired productextracted using ethyl acetate. The extract was taken to dryness, 50 ml.ethanol added, and HCl gas admitted, thereby precipitating 5.5 g. of thehydrochloride of N -methy1-N -(2-methoxyethyl)-2-nitro-pphenylenediamineas yellow crystals; this was filtered off and used as such in dyeingexperiments described below.

Example 10 ITIHCH CH NHCOCH The 56.5 g.N-(Z-aminoethyl)-2,4-dinitroaniline in 300 ml. water, there was added 30g. acetic anhydride. The mixture was heated at 80 C., cooled and thenfiltered. The filter cake obtained was then washed. There was recovered58 g. of acetylated product of the above structure having a meltingpoint 1747 C.

Calcd for C H N O N, 20.9%; found N, 20.7%.

Example 1 l NHCHzCHzNHC CH3 NHz A mixture containing:

1 g. platinum-on-charcoal 100 ml. concentrated HCl 110 ml. ethanol 13.7g. N-(Z-acetamidoethyl)-2,4-dinitroaniline was hydrogenated atatmospheric pressure until 3 molar equivalents of hydrogen wereabsorbed. The reaction mixture was then filtered and the precipitate wasslurried in 100 ml. of water and refiltered for removal of the catalyst.Ammonia was added to the filtrate until it was basic. Violet crystalswere then filtered off which had a melting point of 87-90 C.; theproduct has the above structural formula.

Calcd for C H N O' N, 23.5%; found: N, 23.5%.

. Example 12 1 |IHCHzOHzNHC 00113 A mixture of the dye, N-(2-acetamidoethyl)-2-nitro-pphenylenediamine, 2.5 molar equivalents ofdimethyl sulfate, and 2 molar equivalents of sodium carbonate, in 50%aqueous alcohol, was heated at reflux until no further change wasevident on a paper chromatogram. The alcohol was then distilled off, andthe mixture cooled. The precipitated product, which has the structureformulated above, was filtered off, washed and dried.

Example 13 NHCHZCHZNHC 0 CH3 A mixture of N-(2-acetamidoethy1)-2-nitro-p-phenylenediamine, 3.5 molar equivalents ofethyl iodide, and 2 molar equivalents of sodium carbonate, in 50%aqueous ethanol were heated in an autoclave at 8090 C. for about 14hours. The alcohol was then distilled off, and the product isolated byfiltering and washing. It has the structure formulated above.

Example 14 NHCH2CH2NHC 0 OH;

A mixture of:

13.4 g. N-(2-acetamidoethyl)-2,4-dinitroaniline 60 ml. water 60 ml.isopropanol was heated at 7080 C. While heating this mixture, there wasadded dr'opwise a solution of 4.7 g. sulfur 17.7 g. 60% sodium sulfiideflakes 18 ml. water The reaction mixture was cooled, filtered and theprecipitate obtained was washed with water and recrystallized from 50ml. ethanol. There was obtained 5.0 g. of the product of the abovestructure. This was in the form of orange crystals having a meltingpoint of 198-201 C.

Calcd for C H N O N, 23.5%; found: N, 23.1%.

Example 15 NHCH CH NHO OCH:

Example 16 l non onmnooomom A mixture of:

5 6.5 g. N- (2-aminoethyl)-2,4-dinitroaniline 500 ml. water 3 0 g.propionic anhydride was stirred at room temperature for 30 minutes. Thiswas then heated to C., cooled, and the precipitate which had formed wasfiltered off, washed and dried. The yield was 49.5 g. and the producthad a M.P. of l56-60 C.

Example 17 IIIHCHgCHgNHC OCHrCH;

I NH;

A mixture containing:

1 g. 5% platinum-on-charcoal 10 ml. conc. HCl

14.1 g. N -(2-propionamidoethyl)2,4-dinitroaniline 200 ml. ethanol washydrogenated at about 50 p.s.i. until 3 molar equivalents of H wereabsorbed. A precipitate was formed which was filtered off, slurried inhot water and then refiltered for removal of the catalyst. To thefiltrate was added ammonia. The product which precipitated was filteredoff. There was obtained 4.5 g. of a product in the 15 form of redcrystals which had a melting point of 125-7" C.; it has the structuralformula shown above.

Analysis.-Calcd for C H N O N, 22.2%; found: N, 22.6%

Example 18 IIIHCH C H NECOCH CI-I;

I I(CH CH OH) Into a solution of:

6.3 g. N -(2-propionamidoethyl)-2-nitro-p-phenylenediamine 170 ml.ethanol was bubbled ethylene oxide until a test portion chromatographedon paper was essentially homogeneous. After evaporation of the ethanol,there was otbained a viscous purple liquid which did not crystallize.

Example 19 IIIHCHZCHZNHGOOHZCHQ Into a mixture of:

14.1 g. N-(2-propionamidoethyl)-2,4-dinitroaniline 60 ml. water 60 ml.ethanol heated to a temperature of 70 C. was dropped a solution of:

4.7 g. sulfiur 17.7 g. 60% sodium sulfide flakes 18 ml. water Themixture was cooled and a precipitate was filtered from the reactionmixture. The filter cake was recrystallized from dilute aqueous ethanol;yield 6.9 g.; M.P.

Calcd for C H N O N, 22.2%; found: N, 22.7%.

Example 20 IIIHCH2CHZNHCOOHZCH2CHS I No;

Into a mixture of:

21 g. N (2-aminoethyl)2,4-dinitroaniline 7 g. sodium carbonate 200 ml.benzene at reflux was droped 12 m1. butyryl chloride over a period of 45minutes. The reaction mixture was cooled and filtered and the cake waswashed with water and recrystallized from ethanol. Yield: 18.6 g.; M.P.180l82 C. Calcd for C H N O N, 18.8%; found: N, 19.1%.

Example 21 NHCH CH NHC 0 CH CH GH 16 A mixture of:

1 g. 5% platinum-on-charcoal 10 ml. conc. HCl 200 ml. ethanol 14.8 g.N(2-butyramidoethyl)2,4-dinitroaniline was hydrogenated at about 50 psi.until 3 molar equivalents of hydrogen were absorbed. From the reactionmixture there was isolated 3 g. of the hydrochloride salt of the productof the above structure by filtration and recrystallization from alcohol.It was used as such in the dyeing experiments described below.

Example 22 IIIHCH CH CH NH NHOH CH CH NHC O OH;

I NO,

A mixture of:

g. N-(3-aminopropyl)2,4-dinitroaniline 500 ml. water and ice 90 ml.acetic anhydride was stirred for two hours. The mixture was filtered,and the filter cake was washed and dried. Yield, 90.5 g.; M.P. 149150 C.

Example 24 NHOH GH CH NHO 0 CH I NH,

A mixture of:

l g. 5% platinum-on-charcoal 10 ml. conc. HCl

150 ml. ethanol 14.1 g. N(3-acetamidopropyl)-2,4-dinitroaniline washydrogenated at 50 psi. When 3 molar equivalents of hydrogen had beenabsorbed, the hydrogenation was terminated. The mixture was filtered andthe hydrochloride of the product was extracted from the filter cake withhot Water. After removal of the water, the residue of the hydrochloridewas recrystallized from ethanol; yield 3.1 g.

Analysis.-Calcd for C11H17C1N4O3 (percent): Cl, 12.3; N, 19.4. Found(percent): Cl, 12.6; N, 19.1.

1 7 Example 25 IkHCH CH NHCOCH;

A slurry of 19.6 g. N -(Z-aminoethyl)-2-nitro-p-phenylenediamine in 150ml. water was treated with 10.2 g. acetic anhydride, and the mixturewarmed gently at 40-50 C. for 10 minutes, and then at 80 C. for onehour. After cooling the mixture was basified, extracted with ethylacetate, and the extract dried over anhydrous magnesium sulfate. Theethyl acetate was removed and replaced with 100 ml. ethanol. Dryhydrogen chloride gas was bubbled in, thereby precipitating the yellowcrystals which'are the hydrochloride salt of the above formulatedproduct. They were used as such in dyeing experiments, as describedbelow.

Example 26 ITTHCH:

l lHCH CH NH A mixture of 16.7 g. N -methyl-2-nitro-p-phenylenediamine,40.8 g. 2-bromoethylamine hydrobromide, 175 ml. water, and 75 ml.isopropanol was treated with sodium carbonate until slightly alkaline;10.6 g. being required. To this was added dropwise over one-half hour,at 7580 C., a 25% solution of 4.8 g. sodium hydroxide. After reflux foranother hour, the alcohol was distilled off, the residue cooled, salted,and treated with 2 ml. conc. HCl until just neutral (pH 6-7). Theprecipitate, which was the free base of the product, having the aboveformulated structure, was filtered off, washed with brine, and then withwater. Yield, 12.0 g. of violet crystals, M.P. 62-64 0, havingessentially a single colored component by paper chromatography.

Example 27 IYIHO Ha I IHCH OH NHC 0011 The compound, N -methyl-N-(2-aminoethyl)-2-nitrop-phenylenediamine (product of Example 26), wasacetylated by following the procedure of Example The product, which wasN -methyl-N (Z-acetamidoethyl)-2- nitro-phenylenediamine, was isolatedas violet crystals and was used in the dyeing of hair, as describedbelow.

Example 28 1TIHCH CH CH NHC 00112011N-(3-arninopropyl)-2,4-dinitroaniline was converted to the glycolylderivative by reaction with 1.1 molar equivalent of glycolic acid inbenzene solution in the presence of sodium bisulfate. The mixture washeated at reflux under a benzene-water separator, so that the waterproduced during the reaction was co-distilled with benzene as it wasformed, and removed from the reaction mixture. Heating was continueduntil water no longer distilled ofl.

The reaction mixture was taken to dryness, giving N-(S-glycolamidopropyl)-2,4-dinitroaniline, which was washed with water anddried, and used directly in the next synthetic step.

Example 29 BIIHCHZCHZCHZNHC OCH OHN-(3-glycolamidopropyl)-2,4-dinitroaniline was hydrogenatedcatalytically according to the procedure of Example 11 for reduction ofthe 4-nitro group. The product, N -(3-glycolamidopropyl)-2-nitro pphenylenediamine, was isolated as the red free base.

Example 30 NHCH CH NHC o-@ To 56.5 g. ofN(2-aminoethyl)-2,4-dinitroani1ine in 200 ml. of 5% aqueous NaOH wasslowly added, while stirring, 40 g. of benzoyl chloride. The reactionmixture was then stirred for an additional two hours. The reactionproduct was filtered off and the filter cake was Washed well with water.42 g. of the product, which has the above formulated structure, wasobtained. On recrystallization from aqueous dimethylformamide, it hadthe melting point 188189 C.

Analysis.-Calcd for C H N O N, 17.0%; found: N, 17.0%.

Example 31 I NH A mixture of:

1 g. 5% platinum-on-charcoal 10 m1. conc. HCl 200 ml. ethanol 16.4 g.N-(2-benzamidoethyl)-2,4-dinitroaniline was hydrogenated for absorptionof 3 molar equivalents of hydrogen. The reaction mixture was filteredhot to remove the catalyst. On cooling, the hydrochloride of the aboveformulated product precipitated out and was collected by filtration: 3.1g.; M.P. 231235 C. From the hydrochloride the free base was recovered;red crystals; M.P. 94 C.

Example 32 ITIHCH ClLNHCO-Q l uoH crr on A solution of 5.2 g. N-(Z-benzamidoethyl)-2-nitro-pphenylenediamine in ml. of ethanol washeated at reflux and ethylene oxide was passed in until a test portionwas chromatographically homogeneous. The solvent was evaporated offgiving a thick violet oil which did not crystallize on standing.

19 Example 33 NHOHzCHzNHCO-Q To a mixture of:

10 g. N-(Z-benzamidoethyl)-2,4-dinitroaniline 70 ml. 50% aqueousisopropanol heated to 60 C. was added a solution of:

15 g. 60% sodium sulfide flakes 4.2 g. sulfur 30 ml. water This mixturewas heated for /2 hour and then cooled and filtered; the filter cake waswashed with water. Yield 5.3 g.; M.P. 177-8-1 C.

Example 34 Example 35 l ncmonzonmnoooomN-(El-benzamidopropyl)-2,4-dinitroaniline was hydrogenated by shaking16.4 g. of the material in 200 ml. ethanol, containing 1 gram of 5%platinum-on-charcoal catalyst, and 100 ml. conc. HCl, at about 50 psi.hydrogen, until three molar equivalents of hydrogen were absorbed. Thereaction mixture was filtered to remove the catalyst, and the filtratereduced to a volume of 25 ml. and set in the cold. After some time aprecipitate of 1 g. of the hydrochloride of the above formulated productwas obtained as yellow crystals of M.P. 222-225 C.

Analysis. Calcd. for C H ClN O N, 17.8%. Found: N, 17.9%.

The mother liquor contained considerably more of the product, as shownchromatographically, and this could be recovered in less pure form, andas the free base by basification of the liquor.

Example 36 l NHCH CHzNHz To a mixture of:

19.7 g. N -(2-hydroxyethyl)-2=nitro-p-phenylenediamine 75 ml.isopropanol 20 175 ml. water 61.2 g. 2-bromoethylamine hydrobromideneutralized wtih sodium carbonate to slight alkalinity was addeddropwise at 75 C. to C., over a period of 20 minutes, 6.0 g. sodiumhydroxide in the form of a 25% solution. Refiuxing was continued forone-half hour. Then the alcohol was distilled 01?, and the mixturesalted at room temperature and acidified with hydrochloric acid. Thelight brown precipitate which formed was filtered off, and washed with alittle water. Upon recrystallization from 150 ml. boiling water, therewas obtained 12.0 g. golden yellow crystals of the hydrochloride of N (2hydroxyethyl)-N -(2-aminoethyl) 2 nitro pphenylene; M.P. 193-194 C.,pure by chromatographic analysis.

Example 37 NHCH CH NHcoCeHg,

A mixture of 24.0 g. N (2 hydroxyethyl) N (2- aminoethyl) -2nitro-p-phenylenediamine, 125 ml. 5% aqueous sodium hydroxide and 15.5g. benzoyl chloride was vigorously shaken in a bottle at roomtemperature until the odor of benzoyl chloride had disappeared (about 1hour). The mixture was then warmed at 40-5 0 C. for /2 hour forsaponification of any benzoyloxy group which may have formed. Thereaction product was then filtered off, and was in the form of violetcrystals having the above formulated structure.

Example 38 IITHOH CH CH NHS 020E! A mixture of 24 g.N-(3-aminopropyl)-2,4-dinitroaniline, 11.4 g. methanesulfonyl chloride,9 g. sodium bicarbonate, and ml. ethanol was heated at reflux for 4 /2hours. The product, which precipitated on cooling, was filtered off,washed with hot water and dried. Yield, 11.5 g.; M.P. afterrecrystallization from ethanol, 162- 165 C.

Analysis.Calcd for C H N O S: N, 17.5%. Found: N, 17.3%.

Example 39 ITIHCH OH OHQNHSO CH;

l IHg A method of 3.18 g. N-(3-methylsulfonamidopropyl)-2,4-dinitroaniline, 0.3 g. platinum-on-charcoal (5%), 2 ml. conc. HCl,and ml. ethanol was hydrogenated until three molar equivalents ofhydrogen were absorbed. No precipitate had formed. The catalyst wasfiltered off. The filtrate was evaporated to dryness and the residuedissolved in water. The aqueous solution was then extracted with ethylacetate for removal of the by-product, which is an isomer of the desiredproduct. Afterwards, the solution was made alkaline, and the red dyewhich partly precipitated was extracted from the mixture with ethylacetate. There was obtained 1.8 g. of red dye of the M.P. 1l47 C.,having the structure formulated above.

21 Example 40 The dye, N -(3-methylsulfonamidopropyl) 2nitro-pphenylenediamine, was hydroxyethylated by bubbling ethylene oxidethrough a solution of the dye in ethanol, at reflux temperature. Whensufficient ethylene oxide had been bubbled in, as determinedchromatographically by the appearance of a maximum of a bluish violetspot, the reaction mixture was taken to dryness. The residue wasrecrystallized from aqueous dimethylformamide, and appeared as darkviolet crystals; it has the above designated structure.

Example 41 To a solution of 21 g.N-(3-methylsulfonamidopropyl)-2,4-dinitroaniline in 150 ml. ethanol wasadded a polysulfide solution prepared from 14.7 g. sodium sulfide and3.9 g. sulfur dissolved in 45 ml. water. The addition was carried out at7080 C. over a period of onehalf hour, and heating was continued for anadditional one-half hour. The reaction mixture was then poured on ice,and the precipitate collected by filtration, washed with water anddried. It was recrystallized from ethanol; yield, 11.6 g.; M.P. 157-160C.

Example 42 NH C Ha I IHOHZCHZNHSOZCEQ N -methylN -(2-aminoethyl) 2nitro-p-phenylenediamine was treated with methanesulfonyl chlorideaccording to the procedure of Example 38. There was obtained a bluishred product, N -methyl-N -(Z-methylsulfonamidoethyl)-2-nitro-p-phenylenediamine.

Example 43 NBC H3 The dye, N -methy1-N -(Z-methylsulfonamidoethyl)-2-nitro-p-phenylenediamine, was hydroxyethylated by following theprocedure of Example 15. There was obtained a bluish violet dye whichdyed hair according to the procedures described below.

Example 44 NHCH CH CH NHSO CH CH CHa 22 A mixture of:

22 g. N(3-aminopropyl)2,4-dinitroaniline 9 g. sodium bicarbonate 15 g.propanesulfonyl chloride ml. ethanol was heated at reflux for 6 hours.The reaction mixture was cooled, filtered and the filter cakerecrystallized from methanol, 5.9 g. of product were obtained; M.P. 2 C.

Analysis.Calcd for C H N O S: N, 16.2%; found N, 16%.

Example 45 NI-ICH CH OH NHS O CH CH CH I NH;

A mixture of:

0.2 g. 5% platinum-on-charcoal 2 m1. conc. HCl

3.46 g. N-(3-propanesulfonamidopropyl)2,4-dinitroaniline 200 ml.methanol Was hydrogenated according to the procedure of Example 11.There was obtained 1.0 g. of the product of the above formulatedstructure, as the free base; M.P. 139-42 C.; M.P. of the hydrochloride215-18 C.

Example 46 A mixture of 22.6 g. N-(Z-aminoethyl)-2,4-dinitroaniline,17.7 g. benzenesulfonyl chloride, 10 g. sodium bicarbonate, and 100 ml.ethanol was heated at reflux for 5 hours. After cooling, the product,having the above formulated structure, was filtered off and washed withwater. Yield, 15.6 g.; M.P. 159-160 C.

Analysis.Calcd. for C H N O S: N, 15.3%; found: N, 15.3

Example 47 IfHCHzCHzNHSOgOGHi I NH,

23 Example 48 IfHCHgCHgNHS 0311 I KGH OH OI-D N -(2benzenesulfonamidoethyl)-2-nitro-p-phenylenediamine was subjected tohydroxyethylation following the procedure of Example 15, in which a hotethanolic solution of the starting material is treated with ethyleneoxide. When the reaction was essentially complete, as shown by a paperchromatogram, the solvent was evaporated off. The residue of reddishviolet dye consisted essentially of the compound of the above formulatedstructure, and was used directly in dyeing experiments as describedbelow.

Example 49 r ncmomonmnc ONH;

A mixture of:

24 g. N(3-aminopropyl)2,4-dinitroaniline 70 g. urea was heated for 5hours at 150 165 C. Water was added to the reaction mixture to dissolvethe excess urea and the reaction mixture was filtered. 12 g. of theproduct was obtained; M.P. 186-9 C.

Example 50 IfHOH CH CH NH C ONH I NH;

A mixture of:

0.2 g. 5% platinum-on-charcoal 2 ml. conc. HCl

150 ml. ethanol 2.83 g. N(3-ureidopropyl)-2,4-dinitroaniline washydrogenated as in the previous examples for reduction of the nitrogroup in the 4-position. The hydrochloride of the product did notseparate by crystallization from the reaction mixture. The mixture ofbases was therefore chromatographed on a silica gel column. Developmentwas eflected by a mixture of 90% CHCl and CH OH. The red band was elutedusing the same solvent mixture, giving 0.7 g. of the product in the formof dark red crystals; M.P. 173-6 C.; it has the above formulatedstructure.

Example 51 ITIHCH CH CH NHC ONH Into a solution of 4 g. N-(3-ureidopropyl)-2-nitro-pphenylenediamine in ethanol at reflux wasbubbled ethylene oxide until a test portion chromatographed on papershowed essentially a single violet band. On evaporation to dryness therewas obtained a violet viscous product which was used directly in. thedyeing of hair, described below.

24 Example 52 IIIHCH CHgCH NHC ONH I NO;

To a solution of 28 g. N-(S-ureidopropyl)-2,4-dinitroaniline in 75 ml.50% isopropanol maintained at 75 C. was added dropwise, over one-halfhour; a solution of 19.3 g. fused 60% sodium sulfide flakes and 5.1 g.sulfur in 30 ml. water. After additional heating for one-half hour andcooling, there precipitated the product, of the above designatedstructure; it was filtered off, washed with water and dried. The orangeproduct was used as such in the dyeing of hair, as described below.

Example 53 IITHCH CH NHC ONH 1503 A mixture ofN-(Z-aminoethyl)-2,4-dinitroaniline and 5 molar equivalents of urea wasfused at l50160 C. for 5 hours. The excess urea was then extracted withwater, and the product was filtered, thoroughly washed and dried. It wasused as such in the next synthetic step.

Example 54 $HCH CH NHC ONH;

I IH N-(Z-ureidoethyl)-2,4-dinitroaniline was reduced catalyticallyaccording to the procedure of Example 50. The product was separatedchromatographically on a silica gel column as in that example, and wasobtained as red crystals having the above formulated structure.

Example 55 IIIHCHZOHZNHC S NH,

To a mixture of 7.6 g. carbon disulfide and 4.0 g. sodium hydroxide inml. water was added portionwise 22.6 g.N-(Z-aminoethyl)-2,4-dinitroaniline with vigorous stirring andoccasional cooling. When addition was complete, the reaction mixture waswarmed at -90 C. for about 2 hours. It was then allowed to cool to 34-40C., and 10.8 g. ethyl chloroformate was added dropwise with no furthertemperature control. The reaction mixture was stirred until the exothermwas complete and the mixture had cooled down to room temperature. Theprecipitated solid, 2-(2,4-dinitroanilino)ethyl isothiocyanate, wasfiltered 01f, washed with aqueous alcohol and water and dried.

The above isothiocyanate was dissolved in ethanol and dry ammonia gaswas bubbled through the solution. The exotherm brought the solution toreflux temperature, and it was allowed to reflux for an additional hour.Part of the alcohol was then distilled off, the mixture poured on ice,and the product collected by filtration, and washed with water anddried. The product was N-(2-thioureidoethyl)2,4-dinitroaniline havingthe above formulated structure, and was used directly in the nextsynthetic step.

25 Example 6 IIIHCH CH NHC SNH,

I NH,

The compound, N-(2-thioureidoethyl) 2,4 dinitroaniline (product ofExample 55), was reduced catalytically according to the procedure ofExample 50. In this case also the hydrochloride of the product did notcrystallize out of the reaction mixture. The reaction mixture, afterremoval of the catalyst, was therefore made basic with ammonia, andextracted with ethyl acetate for recovery of the mixed primary aminesobtained. The mixed amines were chromatographed on a column of silicagel, using chloroformmethanol 9:1 for developement. The red band was cutout of the column and the product extracted therefrom. It appeared asdark red crystals and had the above designated structure.

Example 57 NHCHgCHgNHC OgCgHi l NO;

N-(Z-aminoethyl)-2,4-dinitroaniline was treated with one molarequivalent of ethyl chloroformate in pyridine solution by stirring themixture of components at room temperature for about one hour. Thereaction mixture was then drowned in water and the precipitated productN (2 carbethoxyaminoethyl) 2,4 dinitroaniline, filtered off, washed anddried.

Example 58 IIIHCHZCHQNHC OgCgHi The compound, N-(Zcarbethoxyaminoethyl)-2,4-dinitroaniline was hydrogenated according tothe procedure of Example 24. The hydrochloride of the product having theabove formulated structure was recovered as yellow crystals, and wasused directly in the dyeing experiments described below.

Example 59 111K 0 H3O H SO Na To a solution of 62.5 g. taurine and 4.2g. sodium bicarbonate in 400 ml. water heated at reflux was added slowly101 g. 2,4 dinitrochlorobenzene. Heating was continued for an additional3 hours. After cooling, the precipitated crystals were filtered 01f,pressed dry and recrystallized from hot water containing a small amount(about 1%) of sodium hydroxide. The product is N-(Z-sulfoethyl)-2,4-dinitroaniline.

Example 60 NHCHQCHZS O NH,

To a slurry of 20 g. N (2 sulfoethyl) 2,4 dinitroaniline in ml. dryxylene was added 15 g. PCl and the mixture was heated at reflux for 5hours. The reaction mixture was then poured on ice, and the precipitatefiltered off. The filter cake was pressed dry, then stirred with anexcess of conc. aqueous ammonia overnight at room temperature. Theproduct was filtered oil and recrystallized twice from water. There wasobtained 1.8 g. of N (2 sulfamoylethyl) 2,4 dinitroaniline; M.P. -9 C.

Analysis.Calcd for C H N O S (percent): N, 19.3; S, 11.0. Found(percent): N, 18.7; S, 10.7.

Example 61 NHCH O H S ozNHg To a solution of 7.3 g. N (2sulfamoylethyl-2,4-dinitroaniline in 20 ml. 50% isopropanol at 70 C. wasadded with stirring over a period of 20 minutes a solution of 6.3 g. 60%sodium sulfide flakes, and 1.7 g. sulfur in 10 ml. water. Heating Wascontinued for an additional one-half hour. On cooling, the product,which had the above formulated structure, precipitated out and wasfiltered off. It was recrystallized from ethanol; dark orange crystals,M.P. 216-218 C.

Example 62 NHCHzCHzSOzNHz Example 6 3 111110 HzGHzS OzNHz M TQZ The dye,N (2 sulfamoylethyl) 2 nitro-p-phenylenediamine was treated with 2.5molar equivalents of dimethyl sulfate and 2 molar equivalents of sodiumcarbonate in 50% aqueous ethanol. The mixture was heated at reflux untilno further change was observed in the 27 chromatogram. Afterdistillation of most of the alcohol, the product was recovered byfiltration; it was washed and dried. The dark violet product was used assuch for the dyeing of hair, as described below.

Example 64 IIIHCHzCHzSOzNHCHa The procedure of Example 60 was followedexcept that in place of ammonia there was used an excess of 40% aqueousmethylamine. The product was N-[Z-(methylsulfamoyl) ethyl]-2,4dinitroaniline.

Example 65 IIIHCH O H S O NHC H3 The procedure of Example 62 wasfollowed except that the dinitroaniline derivative used was N-[2-(methylsulfamoyl)ethyl]-2,4-dinitroaniline. The product was thehydrochloride of the dye of the above formulated structure. 9

This salt was used directly in the subsequent hair dyeing experiments,described below.

Example 66 IIIHCH CILS OZNIEI CHZO H 0 11 The procedure of Example 60was followed except that in place of ammonia there was used an excess of50% aqueous ethanolamine. The product was N-[2-(2-hydroxyethylsulfamoyl)ethyl]-2,4-dinitroaniline and was used inthe next example.

Example 67 IYIHCH CH S O NHCH GH OH I IHg The procedure of Example 62was followed except that the dinitroaniline derivative used wasN-[2-(2-hydroxyethylsulfamoyl)ethyl]-2,4-dinitroaniline. The product wasthe hydrochloride of the dye having the above formulated structure. Theyellow hydrochloride product was used in the later hair dyeingexperiments.

Example 68 IIIHCHZCHQS O N(CH3)g The procedure of Example 60 wasfollowed, except that in place of ammonia there was used an excess of25% aqueous dimethylamine. The product wasN-[2-(dimethylsulfamoyl)ethyl]-2,4-dinitroaniline. It was used in thefollowing example.

28 Example 69 IITHCH CH S O N(CH CH OH) 1 102 The procedure of Example60 was followed, except that in place of ammonia there was used 25%aqueous diethanolamine. The product wasN-[Z-(bis-Z-hydroxyethylsulfamoyl)ethyl]-2,4-dinitroaniline.

Example 71 lfrroH oH so NwH oH om The compound,N-[2-(bis-Z-hydroxyethylsulfamoyl)- ethyl] -2,4-dinitroaniline washydrogenated according to the procedure of Example 62. There wasobtained the hydrochloride of the base whose structure is formulatedabove. It was used in this form for the dyeing of hair, as describedbelow.

Example 71A ITIHCH GH SO N OH CH OH NO The procedure of Example 60 wasfollowed except that in place of ammonia there was used 25 aqueous 2-methylaminoethanol. The product was N-[2(N-methyl-N-2-hydroxyethylsulfamoyl) ethyl] -2,4-dinitroaniline.

Example 7 l B 0 H ITTHC HZCHZSOZN CHgOHgOH NO l IHQ The compoundN-[2(N-methyl-N-Z-hydroxyethylsulfamoyl)ethyl]-2,4-dinitroaniline washydrogenated according to the procedure of Example 62. There wasobtained the hydrochloride of the base whose structure is formulatedabove. It was used in this form for the dyeing of hair, as describedbelow.

Example 72 NI'IC H 11 s 0 C 1r;

Example 73 Nnon on so om The compoundN-(Z-methylsulfonylethyl)-2,4-dinitroaniline was hydrogenated accordingto the procedure of Example 47. The product, of the structure formulatedabove, was isolated as the yellow hydrochloride as in that example. Itwas chromatographically pure, and was converted to the red free base forthe dyeing experiments performed on hair, which are described below.

Example 74 I vHOHQ NHCHZCHZC OCH3 A solution of N-methyl-2-nitro-p-phenylenediamine and 5 g. methyl vinyl ketone in 100ml. ethanol was heated at reflux for 5 hours. The chromatogram at thispoint showed a single, violet component to be present. The reactionmixture was clarified, and concentrated to 75 ml. On cooling, theproduct, which had the above formulated structure, crystallized out.There was obtained 5 g. of red crystals of M.P. 120123 C., which wasessentially pure by chromatogram.

Calcd for C H N O N, 17.7%; found: N, 17.2%.

Example 75 1 IHO H:

| HOOH CH NCH CH C OCH;

The dye, N -methyl-N-(3-oxobutyl)-2-nitro-p-phenylenediamine (product ofExample 74) was hydroxyethylated by treatment with ethylene oxideaccording to the procedure of Example 15, except that methanol was usedas the solvent instead of ethanol. When the reaction was terminated, asindicated by no further change in a chromatographic test, the reactionmixture was chromatographed on a silica gel column, developing with amethanolchloroform 1:9 mixture. The product, having the structureformulated above, was recovered from the bluish violet band found on thecolumn, and was used for the dyeing of hair as described below.

Example 76 a I MCH CI-LCOCHQ A mixture of 15.3 g.Z-nitro-p-phenylenediamine, 14 g. methyl vinyl ketone, and 150 ml.ethanol was heated at reflux for 8 hours. Afterwards it was allowed tocool over night, and the crystalline precipitate filtered off. Thesecrystals showed a single, violet band when examined chromatographically.They were recrystallized from ethanol, giving 15 g. violet crystals,M.P. -7 C.

Analysis.--Calcd for C H N O (percent): C, 57.4; H, 6.48; N, 14.3. Found(percent): C, 57.4; H, 6.73; N, 14.0.

Example 77 ITTHCHzGHzOH The hydrochloride of N-(2-hydroxyethyl)-2-nitro-p phenylenediamine was treated with 4 molarequivalents of methyl vinyl ketone in alcohol under reflux. When thereaction was essentially complete, the mixture was concentrated to asmall volume and, on cooling, the product which has the structuredesignated above, precipitated out, and was filtered off. The purplecrystals were used to dye hair as described in later examples.

Example 78 NHC H3 The compound, N -methyl-2-nitro-p-phenylenediamine,was treated with 4 molar equivalents of hydroxymethyl vinyl ketoneaccording to the conditions and procedure of Example 76. There wasobtained the product having the above formulated structure as a violetpowder which was used in the dyeing experiment described below.

Example 79 I NHOHzCN A mixture of:

15.3 g. 2-nitro-p-phenylenediamine 47.4 g. pyridine 75 ml. isopropanolwas heated under reflux at 92 C., and over a period of 20 minutes, 45.2g. of chloroacetonitrile was added dropwise at this temperature. Afteran additional 15 minutes at reflux, the mixture was allowed to cool,diluted with three volumes of water and salted with NaCl. Thecrystalline substance which separated out was filtered off, washed withwater and recrystallized from 1500 ml. of boiling 31 water, with theaddition of some active carbon. The yield of product, having the aboveformulated structure was 8.5 g.; M.P. 151-l52 C. It was essentially pureby paper chromatography.

Example 80 IIIHCH OH OH I NHCHZON To a mixture of:

19.7 g. N -(2-hydroxyethyl)-2-nitro-p-phenylenediamine 75 ml.isopropanol 47.4 g. pyridine was added dropwise, at reflux during /2hour 45.3 g. chloroacetonitrile. After refluxing for another /2 hour,the reaction mixture was diluted with two volumes of water and onevolume of ice and some salt added. The crystalline product whichprecipitated was filtered OE, and washed to neutrality with cold water.The wet cake was then recrystallized from 1350 ml. of boiling water,with the addition of active carbon. Yield; 13.2 g. of black crystals;M.P. 1202 C.

Analysis.Calcd for C H N O N, 23.7%; found: N, 23.1%

Example 81 A mixture of:

30.6 g. 2-nitro-p-phenylenediarnine 20 g. calcium carbonate 27 g.3-bromopropionitrile 500 m1. benzene was heated at reflux for 13 hours.On cooling there crystallized out a red product, which was recovered byfiltration and recrystallized from ethyl acetate; M.P. 132-l33 C. Thiswas the compound shown structurally above.

Analysis.Calcd for C H N O N, 27.2%; found: 27.6%.

Example 82 IIIHCH CH OH I IHCH CH CN A mixture of:

9.86 g. N -(2-hydroxyethyl)-2-nitro-p-phenylenediamine 20.1 g. Ii-bromopropionitrile 3.0 g. Na CO anhydrous 50 ml. isopropanol 35 ml.water was heated at reflux for 5 hours. After about 2 hours more Na CO(2.5 g.) and more bromopropionitrile (5 g.) were added. When thereaction was complete, the mixture was diluted with 50 ml. water, andallowed to stand overnight. Crystals of product separated (5.2 g.crude), which were recrystallized first from 1:3 ethanol- -water andthen from 96% ethanol. Yield: 3.5 g. of small metallic crystals, M.P.6970 C. The product which has the structure designated above, washomogeneous by chromatogram.

32 Analysis.Calcd for C H N O N, 22.4%; found: N, 22.4%.

Example 83 NHCHZCHZOH HOCH CH NCH CH CN A mixture of 4.38 g. of the dye,N -(2-hydroxyethyl)- N -(2-cyanoethyl)-2-nitro-p-phenylenediamine, 6.04g. 2- chloroethanol, 2.5 g. calcium carbonate and 24 ml. water,containing catalytic amounts of iodine and cuprous chloride was heatedat reflux for 12 hours. The reaction mixture was then acidified,clarified, diluted with three volumes of water, and made alkaline. Uponcooling, the product precipitated, and was collected by filtration; M.P.1 11-1 13 C.

Example 84 IITHCH:

I NHCH OILCN A mixture of:

8.26 g. N -methyl-2-nitro-p-phenylenediamine 33.5 g.3-bromopropionitrile 6.0 g. anhydrous sodium carbonate in 35 ml. waterand 50 ml. isopropanol was heated at reflux. After about 2 hoursadditional sodium carbonate (2.5 g.) and bromopropionitrile (10 g.) wereadded. The total time of refluxing was 5 hours. On cooling and standingovernight crystals separated, which were filtered off and washed byslurrying in 250 ml. water. Yield: 5.4 g. of small metallic needles,M.P. 132134 C. The product which has the above formulated structureshowed a single, violet component by chromatogram.

AnaZysis.Calcd for C10H12N402: N, found: N, 25.1%.

Example 85 IIIHCH;

HOCHZCHZ NCHQGHZON The dye, N -methyl-N-(Z-cyanoethyl)-2-nitro-p-phenylenediamine (product of Example 84) washydroxyethylated by treating it in 50% aqueous ethanol with 3 molarequivalents of ethylene chlorohydrin in the presence of 1.5 molarequivalents of calcium carbonate. The reaction slurry was stirred atreflux temperature until a chromatographic test showed no furtherchange. The mixture was then cooled, acidified to dissolve anycalciferous residue, and steam-distilled for removal of the excesschlorohydrin. On basifying and salting, the product, which has thestructure formulated above, was precipitated and was recovered byfiltering and washing, as violet crystals.

The following examples illustrate the dyeing of hair with compositionscontaining the dyes described above. The dyeing procedures used areidentified as follows:

LDYEING PROCEDURE A Dyeing hair with alkaline compositions (pH 7 orhigher) A mixture was prepared using specified amounts of the followingcomponents:

Dye (the product of an previous example)=amount to be specified 33Isopropanol0.5 ml. Alkaline agent--amount to be specified Surface-activeagentamount to be specified Thickening agentamount to be specified Thedye was first wet with isopropanol and the above listed agents wereadded, as well as 50 ml. water. The mixture was then heated at 60 C.with stirring until a uniform dispersion was obtained. The mixture wasthen further diluted with water to a volume of 100 ml. and citric acidwas added to give a final, specified pH of 7 or higher. The dyeingcomposition so obtained was poured on natural gray hair and on bleachedhair and allowed to remain in contact with the hair for 20 minutes at 30C. Afterwards, the hair was rinsed in clear water and dried.

DYEING PROCEDURE B Dyeing hair with acid compositions (pH 7 or lower) Amixture was prepared as follows:

Dye-amount to be specified Isopropanol0.5 ml.

Surface-active agent-amount to be specified Thickening agentamount to bespecified Water-to 100 ml.

Acid agentto give specified pH of 7 or lower The dye was wet withisopropanol, and the other ingredients added with stirring and warmingbelow 50 C. to give a uniform dispersion. Hair was dyed with thiscomposition as in Procedure A.

PROCEDURE C Dyeing hair from peroxide bath The following composition wasprepared:

Dye0.75 g.

Isopropanol2.5 ml.

Oleic acid-35.0 g.

Polyoxyethylene, monooleate (Tween 80)10.0 g.

Isoo :tyl phenylpolyethoxyethanol (Triton X100)Ethylenediaminetetraacetic acid0.25 g.

28% ammonia10.0 ml.

Water-to 100 ml.

A 30-ml. portion of this composition was mixed with 30 ml. of 6%hydrogen peroxide and the mixture poured on natural gray and bleachedhair and allowed to remain there for 40 minutes at 30 C. The hair wasthen rinsed with clear water, shampooed and dried.

Example 86 The product of Example 2 was dyed on hair according toProcedure A, using 0.25 g. dye, 3.0 g. N-phenyldiethanolamine (asalkaline agent), 3.0 g. sodium N-coconut acid N-methyl taurate (assurfactant), and 3.0 g. hydroxyethylcellulose (as thickener), the pHbeing adjusted to 9.5. Both gray and bleached hair were dyed in stronglevel orange shades fast to shampooing. When this composition was storedfor 3 months at 50 C. and again dyed on hair, the deyings were fullyequivalent to the initial dyeings in shade and strength.

When the same dye was applied according to Procedure B, using 0.25 g.dye, 1.0 g. nonylphenox'ypoly(ethyleneoxy)ethanol (surfactant), 2.0 g.hydroxyethylcellulose (thickener) and citric acid to pH 5, the gray andbleached hair were also dyed uniformly and strongly in orange shade,stable to shampooing. This composition was also unaifected by storage at50 C. for 3 months.

When the dye was applied by Procedure C, it gave similar orange shadesas above, showing its stability to peroxide.

Example 87 The product of Example 3 was dyed on hair accord ing toProcedure A, using 0.3 g. dye, 3.0 g. diethylenetriamine (alkalineagent), 4.0 g. lauric diethanolamide (surfactant) and 3.0 g.methylcellulose (thickener), the pH being adjusted to 8.5. A red dyeingof good strength was obtained, somewhat stronger on the bleached than onthe gray hair, and both fast to shampooing. When the above compositionwas stored at 50 C. for 3 months and then again dyed on hair, thedyeings were similar in shade and strength to the initial dyeings.

Example 88 The product of Example 8 was dyed on hair according toProcedure A, using 0.15 g. dye, 4.0 g. ethanolamine (alkaline agents),2.0 g. sodium dodecylbenzenesulfonate, and 3.0 g. sodiumcarboxymethylcellulose, the final pH being 8.0. Both gray and bleachedhair were dyed similar shades of bluish violet having good fastness toshampooing and rubbing. The dye composition was also stored at 50 C. for3 months and thereafter dyed hair identically to the initial dyeing inshade and strength.

When Procedure B was used with the same dye, using 0.4 g. dye, 2.0 g.ethyleneglycolmonostearate, 2.0 g. methylcellulose, and lactic acid topH 5.5, the bleached hair was dyed strongly and the gray hairmoderately, in level bluish violet shades, fast to shampooing.

Example 89 The dye which is the product of Example 14 was appliedaccording to Procedure A, using 0.2 g. dye, 3.0 g. isopropanolamine asthe alkaline agent, 4.0 g. coconut acid monoethanolamide (surfactant),3.0 g. hydroxyethylcellulose, and citric acid to pH 7.5. The dyeingswere strong orange shades, similar on both kinds of hair, and fast toshampooing and rubbing. When the pH was adjusted to 9.5, the dyeingswere similar.

The same dye was applied to Procedure B using the same quantity of dye,3.0 g. polyoxyethylated nonylphenol and 3.0 g. meth'ylcellulose, andacetic acid to pH 6.0. Orange dyeings of good strength and uniformitywere obtained, fast to shampooing.

When the dye was applied to Procedure C, it also gave strong orangedyeing on both gray and bleached hair from the peroxide bath, equal tothe above dyeing applied without peroxide.

Example 90 The product of Example 17 was dyed according to Procedure A,using 0.1 g. dye, 4.0 g. triethanolamine (alkali), 0.75 g. sodium Nmethyl-N-oleoyltaurate (surfactant) and 3.0 g. sodiumcarboxymethylcellulose, and adjusting the pH to 10. A heavy red shade onboth kinds of hair was obtained which was only slightly reduced after 3shampooings. The dye composition was stable on storage at 50 C. for 3months; thereafter it dyed hair in the same shade and strength asinitially.

When Procedure A was followed using 0.1 g. of the same dye, 0.2 g.triet-hanolamine (as alkali), 4.0 g. coconut monoethanolamide, and 4.0g. polyethyleneoxy stearate as surfactants, and adjusting the pH to 7.0,a red shade again was obtained, slightly weaker than the above shade,but remarkably level, and about equal on both kinds of hair.

By following Procedure B, and using 0.1 g. of the same dye, 1.0 g.isooctylphenyl polyethoxy ethanol, and no thickening agent, andadjusting the pH to 5.5 by addition of acetic acid, there was againobtained a strong red dyeing, somewhat stronger on bleached than on grayhair, and fast to shampooing and rubbing.

Procedure C was followed with 0.1 g. of the same dye and gave a reddyeing somewhat weaker than the dyeing mentioned in the first paragraph,but still moderately strong and uniform on both kinds of hair.

Example 91 The dye product of Example 24 was dyed according to ProcedureA: 0.2 g. dye was combined with 3 g. ethanolamine (alkali), 3 g. sodiumN-coconut acid N-methyl taurate (surfactant) and 2 g. methylcellulose,at pH 8.5. The dyeings were strong reds on both gray and bleached hair,fast to shampooing and rubbing. When, by Procedure A, 0.2 g. dye wascombined with 4 g. 3,3'-imino dipropylamine, 2 g. sodium lauryl sulfateand 3 g. methylcellulose at pH 9.5, very similar dyeings were obtained.Again, by Procedure A, for 0.2 g. dye, using 9 g. 28% ammonia as thealkaline agent, 20 g. oleic acid, 1 g. sodium lauryl sulfate and 3 g.polyethoxylated nonylphenol as the surfactants, at pH 9.5, the dyeingswere somewhat weaker than the preceding dyeings, but still strong redson both kinds of hair.

The same dye was applied by Procedure B, in the following compositions:(a) 0.25 g. dye, 3 g. polyethoxylatednonylphenol, 3 g. methylcellulose,and sulfuric acid added to pH 5; (b) 0.25 g. dye, 0.5 g. ethyleneglycolmonostearate, 2 g. dicoco dimethyl ammonium chloride, 1 g. cetyl stearylalcohol, and citric acid added to pH 7. Red dyeings were obtained inboth kinds of hair, of same shade, and almost as strong, as the firstdyeing above obtained by Procedure A. The dyeings were fast toshampooing and rubbing.

The same dye (0.25 g.) was also applied by Procedure C, and in spite ofthe presence of peroxide gave strong red dyeings of gray and bleachedhair.

Example 92 The dye product of Example 32 was dyed by Procedure A, using0.25 g. dye, 2.0 g. N-phenyldiethanolamine (alkali), 3.0 g. coconutdiethanolamide (surfactant) and 1.0 g. co-polymer of acrylic acid andallylsucrose (thickener) the pH being set at 9.0. The color on hair wasbluish violet, the affinity being high on gray hair and very high onbleached. Shampoo fastness was excellent. The dye bath stored at 50 C.,for 3 months, gave no change in shade and strength of dyeing thereafter.

The same dye by Procedure B, using 0.25 g. dye, 2.0 g. ethyleneglycolmonostearate (surfactant) and ammonium sulfate added to give a pH of5.0, gave a strong bluish violet dyeing of bleached hair, somewhatweaker on gray hair, both dyeings being fast to shampooing and rubbing.

When Procedure B was followed using 0.25 g. dye and 2.0 g. distearyldimethyl ammonium chloride and 1.5 g. cetyl-stearyl alcohol assurfactants, with no thickener, the pH being adjusted to 7 by means ofcitric acid, there was obtained a strong dyeing of the bleached hair inbluish violet shade; the gray hair was dyed a weaker but level shade ofbluish violet, both dyeing being fast to shampooing and rubbing.

Example 93 The dye product of Example 41 was applied to hair byProcedure A, using 0.15 g. dye, 3.5 g. 1,3-diaminopropane (as alkalineagent), 1.0 g. sodium lignosulfonate (surfactant), and 3.0 g.hydroxyethylcellulose (thickener and setting the pH at 8.0. Both grayand bleached hair were dyed equally strong shades of orange, very fastto successive shampooings. The dye bath was stable on 3 months storageat 50 C.

By Procedure B, this dye, 0.2 g., with 2.0 g. polyethoxylated octylphenol and 2.0 g. hydroxyethylcellulose at a pH of 6.5 effected byaddition of formic acid, gave equal uniform orange dyeings of the twokinds of hair fast to shampooing.

Example 94 The product of Example 50 was dyed by Procedure A using 0.1g. dye, 2.0 g. 3,3'-imino-dipropylamine (as alkaline agent), 3.0 g.mixed fatty acids diethanolamide (as surfactant), and 2.0 g. sodiumalginate (as thickener), the pH being adjusted to 9.0. The gray andbleached hair were both dyed a similar, level red shade of goodstrength, which was fast to successive shampoos. The dye compositionsremained unchanged after three months storage at 50 C., after which timeit dyed hair in the same shade and strength as initially.

Procedure A was again followed with this dye, using 0.1 g. dye, 1.5 g.diethylenetriamine (alkaline agent), 2.0 g. N-lauryl myristylbeta-aminopropionic acid (surfactant), and 1.0 g. methylcellulose, at apH of 8.0. The dyeings were similar to those above.

In a third dyeing by Procedure A, 0.1 g. of the same dye, was combinedwith 2.5 g. morpholine (alkaline agent), 2.0 g. dodecylbenzenesulfonate(surfactant) and 1.0 g. copolymer of acrylic acid and allylsucrose(thickener) at a pH of 9.5. The dyeings were similar to those above.

Example The dye product of Example 61 was applied to hair by ProcedureA, using 0.2 g. dye, 1.5 g. ethylenediamine (alkaline agent), 0.75 g.sodium lauryl sulfate surfactant), and 2.5 g. sodiumcarboxymethylcellulose, at a pH of 9.5. A strong level orange dyeing wasobtained on both kinds of hair, fast to shampooing and rubbing.

When dyed by Procedure B, with 0.2 g. dye, 3.0 g. cetylpyridiniumbromide(surfactant), 1.5 g. methylcellulose and tartaric acid added topH 6.5, the dyeings were slightly stronger than the above dyeings, butequally level and uniform as between the two kinds of hair.

The same dye was applied by Procedure C in which case it gave stronglevel dyeings. The shade and strength were the same as when the dye wasapplied without the use of hydrogen peroxide, substituting an equalvolume of water.

Example 96 The product of Example 62 was dyed variously according to-Procedure A, using 0.25 g. dye. In one case the alkaline agent was 0.5g. triethanolamine, the surfactant was 2.0 g. sodiumN-oleoyl-N-methyltaurate, and the thickening agent was 3.0 g. sodiumcarboxymethylcellulose, the pH being adjusted to 7.5. In another casethere was used 2.0 g. N-phenyldiethanolamine 2.5 g. polyoxyethylenelauric ester, and 3.0 g. sodium carboxymethylcellulose; and the pH was8.5. In both cases very similar red dyeings were obtained, of about thesame shade and strength on the two kinds of hair, and fast toshampooing.

Example 97 The dye product of Example 74 was applied to hair byProcedure A using 0.15 g. dye, 3.0 g. diisopropanolamine, 3.0 g. lauricdiethanolamide, and 3.0 g. methylcellulose, at pH 8.5. An excellentmaroon dyeing was obtained of high strength and levelness, fast to threesuccessive shampooings. When in this procedure there was used 2.0 g.1,3-diaminopropane, 3.0 g. glyceryl stearate and 3.0 g. methylcellulose,at pH 9.0, the dyeings were essentially similar in shade, strength andfastness. When the above dye compositions were stored at 50 C. for 3months and then dyed on hair again, the dyeings were similar to theinitial dyeings in shade and strength.

The dye was also applied by Procedure B using 0.15 g. dye, 2.0 g.ethylene glycol monostearate, and lactic acid added to give pH 5.0. Thebleached hair was dyed strongly maroon, the gray hair being dyed asimilar but weaker shade. The same procedure was followed using thefollowing ingredients: 1.0 g. polyethoxylated coconut fatty acid amide,3.0 g. di-coco dimethyl ammonium chloride, 2.0 g. hydroxyethylcellulose,and citric acid to give pH 6.5. Moderately strong maroon dyeings wereobtained, with the bleached hair being dyed stronger than the gray.

Example 98 The product of Example 76 was dyed on hair by Pro cedure A,using 0.2 dye and the following adjuvants: 2.5 g. diethylenetriamine,2.0 g. polyoxyethylene lauric ester and 3.0 g. gum arabic; the pH wasadjusted to 8.5. The hair was colored strongly violet, similarly on grayas on bleached hair, and the shampoo fastness was very good. Almost asstrong a violet dyeing was obtained by using the following adjuvants:3.0 g. ethanolamine, 3.0 g. coco- 37 nut fatty acid diethanolamide, and3.0 g. sodium carboxymethylcellulose, at pH 8.5. Somewhat weaker violetdyeings, but still very level and fast to shampooing, were obtained withthe following: 30 g. triisopropanolamine, 3.0 g. coconut fatty aciddiethanolamide and 3.0 g. sodium carboxymethylcellulose, at pH 8.0.

The same dye was also applied by Procedure B using: 0.2 g. dye, 1.5 g.glycerol monooleate and acetic acid added to give a pH of 5.5. A similarshade of violet was obtained which was particularly strong on thebleached hair.

Example 99 The dye product of Example 81 was applied by Procedure Ausing 0.15 g. dye and several combinations of adjuvants, as follows:

(1) 3.0 g. 1,3-diaminopropane, 2.0 g. sodium N-coconut-N-methyl taurate,with no thickener; pH 9.0;

(2) 2.0 g. N-phenyldiethanolamine, 1.5 g. sodium lignosulfonate, and 2.0g. hydroxyethylcellulose; pH 8.0;

(3) 3.0 g. ethanolamine, 1.5 g. sodium lignosulfonate, and 2.0 g.hydroxyethylcellulose; pH 8.5; and

(4) 0.25 g. triisopropanolamine, 4.0 g. coconut acid ethanolamide, 2.0g. coconut acid diethanolamide, 3.0 g. coco amine crotonic acidcondensate; pH 7.5.

The dyeings were all strong level maroon shades, similar in shade andstrength on both kinds of hair. The dyeings (1) above were particularlyheavy, as compared to (2), (3) and (4) which were all essentially alike.

The same dye was also applied by Procedure B using 0.15 g. dye combinedwith the following:

(1) 2.0 g. octylphenol polyethylene oxide condensate; with no thickener,citric acid to pH 5;

(2) 1.0 g. glycerol monostearate, 3.0 g. dodecyl benzyl dimethylammonium chloride; ammonium sulfate added pH 6.5.

38 The dyeings were level maroons, similar on both kinds of hair.Dyeings (l) Were heavier than deyings (2), but both were strong.

Example 100 The product of Example 82 Was dyed on hair by Procedure A,using 0.15 g. dye and the following combinations of adjuvants:

(l) 3.0 g. diethylenetriamine, 1.0 g. sodium dodecylbenzenesulfonate,2.0 g. hydroxyethylcellulose; pH 9.5;

(2) 4.0 g. isopropanolamine, 3.0 g. nonylphenol polyoxyethylenecondensate, 2.0 g. sodium carboxymethylcellulose; pH 8.5.

The dyeings were a purple shade of very good strength, which were fastto three successive shampooings.

The same dye was applied by Procedure B using 0.15 g. dye, combined withthe following:

(1) 1.5 g. polyoxyethylene monostearate, 2.0 g. hydroxyethylcellulose,lactic acid added to pH 6.5;

(2) 2.0 g. cetyl pyridinium bromide, 1.5 g. polyoxyethylated fattyalcohol, citric acid to pH 7.

The dyeings were in moderately strong purple shades, fast to shampooingand rubbing.

The same dye was also applied by Procedure C and gave moderately strongpurple dyeings. The dye was shown to be completely stable in theperoxide composition, since when it was dyed by Procedure C but withoutperoxide (substituting an equal volume of water), it gave the same shadeand strength as when dyed with peroxide.

The following additional dyeings, performed according to Procedure A,are listed in Table I, wherein the various columns designate the dye,the alkaline agent, the surfactant, and the thickening] agent, togetherwith the amount of each component used, the final pH of the composition,the color produced on gray and bleached hair, and any especiallynoteworthy characteristics of the composition or dyeings TABLE IDye-Prodnot of Amount Example of dye, g. Alkaline agent SurfactantThickening agent pI-I Color on hair Comments 4 0.3 5 g.triethylenetetra- 0.5 g. sodium lamyl sulfate. 2 g. methylcellulose 9. 5Bluish violet mine. 4 0.5 do do do 9.5 do

6 0.05 ,2 g. diethanolamine. 1 g. polyethoxylated 1 g. acrylic acida11y1- 9.0 Orange Fast to 3 Shampoos,

nonylphenol. sucrose copolymer.

7 0.25 3 g. N-phenyldiethanol- 4 g. coconut acid 3 g. sodium carboxy-9.0 Red amine. diethauolamide. methylcellulose. 0.5 do d0 ..do 9.0 Red0. 1 1 g. 1,2-diaminopropane 0.5 g. sodium lignosulionatc None 8.0Violet 0,1 1 g. triethylamine 2 g. lauric diethanolamide 2 g.methylccllulose 8. 5 Red Dye bath stable on storage.

0. 2 4 g. triethanolamine 3 sodium N-oleoyl-N- 3 g. sodium carboxy- 9. 5Bluish violct.

methyl taurate. methylcellulose.

0. 2 4 g. triethanolamine. 0.5 g. sodium dioctyl 2 g. sodium carboxy- 0.5 Bluish violet sulfosuccinatc. mcthylcellulose.

0. 3 4 g. 3,3-im.inodipropyl- 1 g. ethylene glycol 3 g. hydroxyethyl- 8.5 Bluish violet amine. monostearate. cellulose. 15 0.75 .do do d0 8.5.do

18 0,15 2 g. morpholine 3 g. polyethexylatcd coco- 3 g.methylcellulose... 9. 5 Bluish violet Fast to 3 shampoos.

nut fatty acid amide. 18 0. 2 0.5g. isopropanolamine-. 2.5 g. coco aminecrotonic None 7. 5 do acid condensate, 3.0 g. coconut aciddiethanolamide.

19 0. 1 2 g. ethylenedlamine.. 2.5 g. sodium lauryl sulfate" 2 g. sodiumalginate 8. 5 Orange Dye bath stable on storage.

21 0.1 2 g. diethylenetriamina. 1.5 g. glyccryl stearate 2 g.methy1ce1lulose 8.0 Red Fast to 3 shampoos.

25 0. 25 3 g. 1,3-diaminopropane- 2 g. sodium lignosulfonate 3 g. sodiumcarboxy- 8. 5 Red methylcellulose.

27 0.25 3 g. triethylenetetra- 3 g. nonylphenoxy poly 3 g. sodiumcarboxy- 9.0 Purple mine. (ethyleneoxy)-ethanol. methyleellulose.

29 0. 25 2 g. 3,3-imino-dlpropyl- 2 g. sodium dodecylbenzenc- 3 g.methylcellulose 8. 5 Red amine. sulfonate.

30 0. 25 2 g. tricthanolamine..... 3 g. sodium lauryl sulfate.. 3 g.methylcellulose. 9. 5 Red TABLE IContinued Dye-Product Amount Example ofdye, g. Alkaline agent Surfactant Thickening agent p11 Color on hairComments 31 0.75 .do do do 9.5 Red 33 0.3 3 g. 1,3-diaminopropaue. 2.5g. sodium N-methyl-N- 3 g. hydroxyethyl- 8. Orange palmitoyl taurate.cellulose.

35 0.25 4 g. tricthanolamine 3 g. polyoxycthylcne lauric 3 g.hydroxyethyl 9. 5 Red ester. cellulose.

37 0.2 3 g. N-phenyldiethanol- 3 g. sodium myristyl sulfate- 2.5 g.sodium earboxy- 9. 5 Violet amine. methylcellulose.

39 0.15 2.5 g. N- phenyldiethan- 3 g. lauric diethanolamide 2 g.methylcellulosc.-- 8. 5 Red Dye bath stable on olamine. storage. 39 0.20.25 g. triisopropanol- 4 g. polyoxyethylcne mono- None 7.0 Red amine.steal-ate, 2 g. coconut acid monoethanolamide, 2 g. coconut aciddiethanolamide.

40 0.2 2 g. isopropanolamin'e. 2 g. sodimn lignosulfonate-.. 3 g. sodiumeai'boxy- 8. 5 Bluish violct methylcellulose.

42 0.25 2 g. ethauolainine 3 g. glyccryl stcarate 1 g. copolymer of 8. 5Purple acrylic acid and allylsucrose.

43 0.25 3 g. N-phenyltriethanol- 3.5 g. sodium nonylnaphth- 3 g.hydroxyethyl- 9.0 Bluish violet amine. alenesulfonate. cellulose.

45 0.3 4 g. isopropanolamine 4 g. lauric diethanolamide... 3 g.fiyilrozyethy- 10.0 Red ce u ose.

47 0.2 3 g. ethylenediamiue 2 g. sodium lauryl sulfate. 3 g.hydr0zyethyl 9.0 Red cellulose.

48 0.1 3 g. ethylenediamine 2 g. sodium lauryl sulfate..- 3 g.hydroxyethyl- 9.0 Bluish violet cellulose.

51 0.25 3 g. dietl1ylenediamine 3 g. nonylphenoxypoly 3 g. hydroxyethyl-9. 5 Bluish violet (ethyleneoxy) ethanol. cellulose.

52 0.15 2 g. N-phenyldiethaol- 2 g. polyethoxylated 3 g. hydroxyethyl-9.0 Orange amine. coconut acid amide. cellulose.

54 0.2 3 g. triethan0lamine 2 g. sodium lauryl sulfate--. 3 g. sodiumcarboxy- 9.0 Red methylcellulose.

56 0.2 3 g. triethanoluminc 2 g. sodium lauryl sulfate 3 g. sodiumcarboxy- 9.0 Red methylcellulose.

58 0.2 3 g. tiethanolamine 2 g. sodium lauryl sulfate... 3 g. sodiumearboxy- 9.0 Red methylcellulosc.

63 0.25 3 g. N-phenyldiethanol- 3 g. polyethoxylated octyl 3 g. sodiumearboxy- 9.0 Bluish violet" amine. phenol. methylcellulose.

65 0.25 4 g. isopropanolaminc" 2,5. sodium N-coeonut 3 g. hydroxyethyl-9. 5 Red acid N -methyl taurate. cellulose.

67 0.25 4 g. isopropanolamine... 2.5 g. sodium N-eoconut 3 g.hydroethyl- 9. 5 Red acid N-methyl taurate. e ulose.

60 0.25 3 g. N-phenyldiethanol- 3 g. polyethoxylated octyl 3g. sodiumearlooxy- 9.0 Red amine. phenol. methylcellulose.

71 0.25 3 g. N-phenyldlethanol- 3 g. polyethoxylated octyl e g. sodiumcarboxyamine. phenol. methylcellulose.

73 0. 25 3 g. triethanolarnine 2.5 g. sodium lauryl sulfate. 3 g. sodiumearboxy- 9.0 Red methylcellulose.

75 0.2 2g. 1, 3-diaminopropano 1.5 g. sodium ligno- 3 g. sodium carboxy-8.0 Violet sulionate. methylcellulose.

77 0.2 3 g. N-phenyldiethanol- 2.5 sodium 1au1'ylsulfate 3 g. sodiumcarboxy- 9.0 Violte.

amine. methylcellulose.

78 0.2 3 g. N-phcuyldiethanol- 2.5 sodium lauryl sulfate 3 g. sodiumearbosy- 9.0 Violet amine. methyleellulose.

79 0.25 3 g. 3, 3-imino-amine 3g. sodium lauryl suliate 3 g. sodiumcarvoxyl- 9.0 Reddish Fast to 3 shampoos.

methylcellulose. brown.

80 0.25 3 g. 3, 3-imino-amine 3 g. sodium lauryl suliate 3 g. sodiumcarboxy- 9.0 Purple Fast to 3 shampoos.

methylcellulose.

83 0.25 1.5 g. isopropanolamine. 2.5 g. sodium dodecyl- 3 g.methylcellulose.- 8.0 Violet benzenesulionate.

84 0.25 3 g. N-phenyldiethanol- 3 g. sodium Nmethyl-N- 3 g. sodiumcarboxy- 9.0 Bluish red Dye bath stable on amine. oleoyl taurate.inethylcellulose. storage.

85 0.25 1.5 g. isopropanolaminc" 2.6 g. sodium dodecyl- 3 g.mcthylcellulose 8. 0 Violet bonzenesulfonate.

The following additional dyeings, performed according and the thickeningagent; together with the amount of each to Procedure B, are listed inTable II, wherein the various component used, the final pH of thecomposition and the columns designate the dye, the acid agent, thesurfactant 7 5 color produced on gray and bleached hair.

